KR20210144807A - Creped multi-ply tissue products - Google Patents

Abstract

A multi-ply tissue product comprising a non-crosslinked binder that is durable, smooth, and has a low level of slough is disclosed. In certain instances, the creped tissue product has a geometric mean tensile (GMT) of from about 700 to about 1,500 g/3″, a basis weight of from about 45 to about 60 gsm, and less than about 2.00 mg, more preferably less than about 1.50 mg. , for example, from about 0.10 to about 2.00 mg, such as from about 0.25 to about 1.50 mg of slough The tissue products of the present invention also have good durability, such as a durability index of about 10.0 to about 20.0, a TS750 value of about 15.0 to 40.0 and have a low stiffness, such as a smooth surface, and a stiffness index of less than about 10.0.

Description

Creped multi-ply tissue products

The present invention relates to a creped multi-ply tissue product.

Absorbent paper products, such as paper towels, cosmetic tissues, and other similar products, are designed to incorporate several important properties. For example, the product should have good bulk, soft to the touch, and be highly absorbent. The product should also have good strength while wet and resist tearing. Unfortunately, it is very difficult to produce high strength paper products that are both soft and highly absorbent. In general, taking measures to improve one characteristic of a product adversely affects other characteristics of the product. For example, softness is typically increased by reducing or reducing fiber bonding in paper products. However, inhibiting or reducing fiber bonding adversely affects the strength of the paper web.

One tissue making process for balancing often competing physical properties is disclosed in US Pat. No. 7,462,258. Processes that may be suitable for printing binder on one or both sides of a web typically include a single creping step. The binder material is a cross-linked latex and includes an azetidinium-reactive polymer. The presence of the azetidinium-reactive polymer allows the binder to crosslink both with itself and with the cellulose of the fibrous web. In this way, the crosslinked latex of the '258 patent forms covalent bonds with the cellulose of the fibrous web. Thus, while the '258 patent discloses an improved process for producing a tissue product with good bulk, flexibility and good absorbency, the resulting product exhibits covalent bonds with the cellulose of the fibrous web that prevent breakage of the web when wet. forming binders.

An alternative to the crosslinked latex binder of the '258 patent is disclosed in US Pat. No. 9,121,137, which discloses a crosslinked latex binder comprising a primary polymer and a polyfunctional aldehyde. The polyfunctional aldehyde, like the azetidinium-reactive polymer of the '258 patent, allows the binder to form covalent bonds with the cellulose of the fibrous web. As such, products produced according to the '137 patent retain a significant portion of their tensile strength after soaking for extended periods of time.

Accordingly, there remains a need in the art for a tissue making process to balance often competing physical properties, such as bulk, hand feel, and absorbency, while also providing a product that can be easily dispersed.

SUMMARY OF THE INVENTION The present invention generally provides a creped tissue web having a durable, flexible, and smooth surface, and articles produced therefrom. The article of the present invention generally comprises two or more tissue webs made by a creping process, more preferably by a printing creping process. The print creping process may be adapted to provide improved durability to the article by disposing a non-crosslinked latex polymer on at least one of the outer surfaces of the tissue article. Surprisingly, however, the presence of the non-crosslinked latex polymer does not negatively affect the stiffness of the article, so that the article generally has a stiffness index of less than about 6.5.

In other instances, the tissue products of the present invention generally have low levels of slough. Slough generally results from the release of loosely bound fibers from the surface of the tissue product in use, and is often a problem when producing soft, low stiffness tissue products. The tissue product of the present invention surprisingly has a low slaw level and low stiffness despite good flexibility. For example, in one embodiment, the present invention provides a creped tissue product, such as a multi-ply creped tissue product comprising two or more plies, having a non-crosslinked latex polymer disposed on at least one of its outer surfaces. A tissue product is provided, wherein the product has a geometric mean tensile (GMT) of from about 800 to about 1,700 g/3″, a basis weight of from about 45 to about 60 gsm, and less than about 2.00 mg, more preferably less than about 1.50 mg, such as about 0.10 to about 2.00 mg, such as about 0.25 to about 1.50 mg of slaw.

In yet another embodiment, the present invention provides a rolled tissue product comprising a helically wound tissue web, wherein the web has a geometric mean tensile strength (GMT) greater than about 700 g/3" and a slough less than about 2.00 mg. has

In another embodiment, the present invention provides a first exterior surface comprising a plurality of embossments and a non-crosslinked latex polymer disposed thereon and a second exterior comprising a non-crosslinked latex polymer disposed thereon. Provided is a rolled tissue product comprising a spirally wound embossed, multi-ply tissue web having a surface, said product having a basis weight of from about 45 to about 60 gsm, a GMT of from about 800 to about 1,700 g/3" and a GMT of from about 0.10 to about Has 2.00 mg of slough.

In other embodiments, the present invention provides a creped multi-ply tissue product comprising a first creped tissue ply and a second creped tissue ply, wherein the product comprises less than about 35, such as about 20 to about 30. a TS750 value, and a stiffness index of less than about 10.0, such as from about 4.0 to about 8.0. In this way, the present invention provides a creped tissue product having a smooth surface and good flexibility. In certain instances, the article is also highly durable, such as having a durability index greater than about 10.0, such as from about 10.0 to about 20.0.

In still other embodiments, the present invention provides a creped multi-ply tissue product comprising: (a) first and second creped tissue ply; (b) a creping composition consisting essentially of a non-crosslinked vinyl acetate-ethylene polymer disposed on said first and second tissue ply and optionally an anti-blocking agent; (c) a polyhydroxy compound having a molecular weight of about 1,000 g/mole, a diamidoamine quaternary compound, an ester quaternary compound, an alkoxy alkyl quaternary compound, benzyl 4 disposed on the first and second tissue ply an emollient composition selected from the group consisting of a tea compound, an alkyl quaternary compound, an imidazolinium quaternary compound, a polysiloxane, glycerin, and combinations thereof; and (d) a plurality of embossments disposed on the first or second ply of tissue; The product has a GMT of about 800 to about 1,700 g/3″, a slaw of about 0.25 to about 1.50 mg, and a TS750 value of less than 40, such as between about 20 and about 40, such as between about 20 and about 30.

1 illustrates one embodiment for forming a multilayer tissue web in accordance with the present invention;
2 depicts one embodiment for forming a basesheet useful in the production of a tissue product according to the present invention;
3 shows one embodiment of a print-crepe process for making a tissue product according to the present invention;
Figure 4 shows one pattern for applying a binder to the basesheet;
5 shows another pattern for applying a binder to the basesheet;
6 shows another pattern for applying a binder to the basesheet;
7 shows a test specimen prepared for the slough test;
8 is a graph of geometric mean tensile strength (GMT, g/3") versus slaw (mg) for commercial ( ) and inventive ( ) articles;
9 is a graph of basis weight (gsm) versus slough (mg) for commercial (-) and inventive (▲) products; and
10 is a graph of Stiffness Index versus TS750 for commercial (●) and inventive (▲) products.

Justice

As used herein, the term "basesheet" refers to those described herein that have not undergone further processing, such as embossing, calendering, treatment with a binder or softening composition, perforation, stacking, folding, or rolling into individual rolled articles. refers to a tissue web formed by any one of the papermaking processes.

As used herein, the term “tissue product” refers to products made from basesheets, and includes bathroom tissues, beauty tissues, paper towels, industrial towels, food service towels, napkins, medical pads, and other similar products. include

As used herein, the term “ply” refers to a separate tissue web used to form a tissue product. The individual plies may be arranged in juxtaposition to each other.

As used herein, the term “layer” refers to a layer of a plurality of fibers, chemical treatments, etc. within a ply. The term “layered tissue web” generally refers to a tissue web formed from two or more layers of an aqueous papermaking stock. In certain instances, the aqueous papermaking stock forming the two or more layers comprises different fiber types.

As used herein, the term “basis weight” generally refers to the quantity per unit area of a tissue and is generally expressed in grams per square meter (gsm). Measure the basis weight as described in the Test Methods section below. Although the basis weight of a tissue product made in accordance with the present invention may vary, in certain embodiments the product may be greater than about 20 gsm, such as greater than about 30 gsm, such as greater than about 40 gsm, such as from about 20 to about 80 gsm, such as from about 30 to about 60 gsm. , such as from about 45 to about 55 gsm.

As used herein, the term “caliper” refers to the thickness of a tissue product, web, sheet or ply, generally in microns (μm), and is measured as described in the Test Methods section below.

As used herein, the term "sheet bulk" is the quotient of caliper (μm) divided by the dry basis weight (gsm). The resulting sheet bulk is expressed in cubic centimeters per gram (cc/g). Tissue products made in accordance with the present invention may in certain embodiments be greater than about 8.0 cc/g, more preferably greater than about 9.0 cc/g, even more preferably greater than about 10.0 cc/g, such as from about 8.0 to about 12.0. It can have a sheet bulk of cc/g.

As used herein, the term "slope" refers to the slope of a line resulting from constructing tension versus elongation, and is the output of MTS TestWorks™ during the determination of tensile strength as described herein in Test Methods. The slope, reported in grams (g) per unit of sample width (inches), is load-corrected, falling within the specimen generating force (0.687 to 1.540 N) of 70 to 157 grams divided by the specimen width. It is measured as the gradient of the least squares line fitted to the strain points.

As used herein, the term “geometric mean slope” (GM Slope) generally refers to the square root of the product of the machine direction slope and the cross machine direction slope. Although the GM slope may vary among tissue products made in accordance with the present invention, in certain embodiments, the tissue product is less than about 10.00 kg, more preferably less than about 9.00 kg, even more preferably about 8.00 kg. It may have a GM slope of less than g, such as from about 6.00 to about 10.0 g, such as from about 6.00 to about 8.00 kg.

As used herein, the term “geometric mean tensile strength (GMT)” refers to the square root of the product of the cross-machine direction tensile strength and the machine direction tensile strength of a web. However, while the GMT of tissue products made in accordance with the present invention can vary, in certain instances the GMT is about 700 g/3″ or greater, such as about 800 g/3″ or greater, such as about 900 g/3″ or greater, such as about 700 to about 1,700 g/3″, such as about 800 to about 1,600 g/3″, such as about 900 to about 1,500 g/3″.

As used herein, the term “stiffness index” is defined as the square root of the product of the slopes of MD and CD (in kg) divided by the geometric mean tensile strength (in g/3”). Refers to the quotient of the average tensile slope.

Although the stiffness index of tissue products made in accordance with the present invention can vary, in certain instances, the stiffness index is less than about 7.0, such as less than about 6.0, such as less than about 5.5, such as from about 4.0 to about 7.0, such as from about 4.0 to about 7.0. about 6.0.

As used herein, the term “TEA index” refers to the geometric mean tensile energy absorption (in units of ^{g cm/cm 2} ) at a given geometric mean tensile strength (in g/3”) as defined by the equation having) refers to:

Although the TEA index may vary, in certain instances a tissue product made in accordance with the present invention has a TEA index of greater than about 1.50, such as greater than about 1.75, such as greater than about 2.00, such as from about 1.50 to about 2.25, such as from about 1.75 to about 2.25. has

As used herein, the term “slaw” generally refers to the undesirable peeling of a piece of tissue web when rubbed and is generally measured as described in the Test Methods section below. Slaw is usually reported as a mass, such as milligrams (mg). Although the slaws of the tissue product of the present invention may vary, in certain instances the tissue product made according to the present invention will be less than about 5.00 mg, more preferably less than about 4.00 mg, such as from about 0.50 to about 5.00, such as from about 0.50 to about 5.00 mg. It has about 4.00 mg of slough.

As used herein, the term "TS750" refers to the smoothness of the surface of a tissue product, generally measured using an EMTEC Tissue Softness Analyzer ("Emtec TSA") (Emtec Electronic GmbH, Leipzig, Germany). and interfaces with a computer running Emtec TSA software (version 3.19 or equivalent). The unit of the TS750 value is dB V ² rms, but in this specification, the TS750 value is often referred to without indicating a unit. In general, the TS750 value is the magnitude of the peak occurring at a frequency of about 200 to 1,000 Hz, which is generated by vibration of the tissue membrane during the test procedure. These vibrations are mainly caused by roughness and embossing. In general, a lower TS750 value indicates a smoother surface.

details

In general, the present invention relates to creped tissue webs, and articles produced therefrom. Creped plies and articles are generally strong, flexible, and have a low amount of slaw. For example, the present invention provides a tissue product having less than about 2.00 mg, more preferably less than about 1.50 mg, such as about 0.20 to about 2.00, such as about 0.50 to about 1.50 mg of slough. Surprisingly, the aforementioned slough levels are achieved despite the product being creped and having a relatively high basis weight, such as ^{greater than about 45 g/m 2} (gsm), such as from about 45 to about 60 gsm.

Typically, increased basis weight, and often associated higher web calipers, negatively impact creping, resulting in higher slough in the final tissue product. A comparison of slough levels of several inventive examples and commercially available tissue products can be found in Table 1 below, and FIGS. 8 and 9 . As shown in the table below, and in the accompanying drawings, the tissue products of the present invention are generally creped and have a relatively high basis weight, such as greater than about 45 gsm, such as less than about 2.00 mg, despite being between about 45 and about 60 gsm, More preferably it has a low amount of slaw of less than about 1.50 mg, such as about 0.20 to about 2.00, such as about 0.50 to about 1.50 mg.

Sample fold air drying creping embossing basis weight (gsm) GMT (g/3") Seat Bulk (cc/g) Slough (mg) Angel Soft 2 N Y Y 37.7 758 8.9 5.9 Charmin Sensitive 2 Y Y Y 43.2 761 10.5 7.2 Charmin Ultra Soft 2 Y Y Y 46.5 715 11.3 5.5 Charmin Ultra Strong 2 Y Y Y 37.2 1102 12.6 11.3 Cottonelle Ultra Comfort Care 2 Y N Y 44.4 990 12.1 7.5 Great Value Ultra Soft 2 Y Y Y 38.5 1050 11.8 4.8 Great Value Ultra Strong 2 Y Y Y 40.0 1347 11.7 10.9 Quilted Northern Ultra Plush 3 N Y Y 52.7 665 9.5 6 Quilted Northern Ultra Soft & Strong 2 N Y Y 42.6 1286 11.2 8.8 Target UP & Up Soft 2 Y Y Y 36.1 802 8.2 3.8 Target Up & Up Ultra Soft 2 Y Y Y 37.1 1101 10.2 7.5 White Cloud Ultra Bath Tissue 2 Y Y Y 48.4 1212 7.6 4 White Cloud Ultra Soft & Strong 2 Y Y Y 37.9 1278 10.9 5.4 Kleenex 2 N Y N 29.7 797 6.0 1.6 Puffs Plus Lotion 2 Y Y N 40.1 874 7.2 6.2 Kleenex Cool Touch 2 N Y N 53.7 985 4.3 5.9 Kleenex Lotion 2 N Y N 42.0 962 4.9 2.9 Puffs Ultra Soft and Strong 2 Y Y N 36.8 1095 7.6 9.9 Invention Example 1 2 Y Y Y 54.6 1255 9.1 0.6 Invention Example 2 2 Y Y Y 53.8 1250 8.3 0.3 Invention example 3 2 Y Y Y 57.4 1380 8.9 1.18

Notwithstanding this trend, the present invention surprisingly provides high basis weight tissue products with low slough. For example, in one embodiment, the present invention provides a creped tissue product, such as a multi-ply creped tissue product comprising two or more plies, the product comprising from about 700 to about 1,800 g/3" has a geometric mean tensile (GMT) of .

In other embodiments, tissue products made in accordance with the present invention have desirable surface properties, such as a relatively high degree of surface smoothness. The tissue products of the present invention have good surface smoothness even when they are embossed. Accordingly, in certain embodiments, the present invention provides an embossed tissue product having an embossing pattern that provides a visually appealing product having good bulk and a relatively smooth surface. For example, a tissue product of the present invention may be embossed and have a TS750 value of less than about 40.0, more preferably less than about 30.0, even more preferably less than about 25.0, such as from about 15.0 to 40.0, such as from about 20.0 to about 35.0. The TS750 value is one measure of the tissue product surface smoothness, with a lower value indicating a smoother surface.

In a particularly preferred embodiment, the tissue product comprises two or more creped tissue webs, wherein at least one of the webs is embossed, wherein the product is less than about 40.0, more preferably less than about 30.0, even more preferably a TS750 value of less than about 25.0, such as from about 15.0 to about 40.0, such as from about 20.0 to about 35.0, and a sheet bulk greater than about 8.0 cc/g, from about 8.0 to about 12.0 cc/g. The aforementioned TS750 values can be achieved at relatively high strengths and materials, such as GMT of about 700 to about 1800 g/3" and basis weight of about 45 to about 60 gsm. Surface Smoothness of Some Inventive and Commercially Available Tissue Products A comparison of can be found in Table 2 below, and in FIGS. 9 and 10 .

Sample fold creping Lotion embossing basis weight (gsm) GMT (g/3") Stiffness index TS750 Charmin Ultra Gentle 2 Y Y Y 43.6 786 7.86 40.0 Charmin Sensitive 2 Y Y Y 37.9 755 7.39 48.8 Cottonelle Gentle Care One N Y N 43.2 761 11.50 102.1 Puffs Plus Lotion 2 Y Y N 40.1 874 13.12 10.8 Kleenex Lotion Facial Tissue 2 Y Y N 42.0 962 15.63 17.9 Kleenex Cooling Lotion Facial Tissue 2 Y Y N 53.7 985 19.11 27.0 Invention Example 1 2 Y Y Y 54.6 1255 6.47 28.3 Invention Example 2 2 Y Y Y 53.8 1250 6.43 31.3 Invention example 3 2 Y Y Y 57.4 1380 5.26 20.8

In still other embodiments, the present invention provides a relatively flexible tissue product, such as a stiffness index of less than about 8.0, such as from about 4.0 to about 8.0, such as from about 4.0 to about 7.0, and a high degree of surface smoothness, such as less than about 40.0, more preferably a TS750 value of less than about 30.0, even more preferably less than about 25.0, such as from about 15.0 to about 40.0, such as from about 20.0 to about 35.0.

In a particularly preferred embodiment, the present invention provides a multi-ply tissue product comprising at least a first and a second creped tissue web, wherein the creped tissue web is disposed on at least one outer surface thereof. -Contains crosslinked latex polymers. The tissue product may further comprise an embossing pattern to provide visual aesthetics and enhance the bulk of the product, such that the product is greater than about 8.0 cc/g, such as greater than about 9.0 cc/g, more preferably greater than about 10.0 cc/g. It is possible to have a sheet bulk greater than g. The tissue product may also include an emollient composition disposed on at least one of its outer surfaces, the emollient composition comprising a polyhydroxy compound having a molecular weight of at least about 1,000 g/mole, a diamidoamine quaternary compound, ester 4 softening compounds selected from the group consisting of tertiary compounds, alkoxy alkyl quaternary compounds, benzyl quaternary compounds, alkyl quaternary compounds, imidazolinium quaternary compounds, polysiloxanes, glycerin, and combinations thereof. Generally, the aforementioned articles have a high degree of surface smoothness, such as a TS750 value of less than 40.0, more preferably less than about 30.0, and a low level of slough, such as less than about 2.00 mg, more preferably less than about 1.50 mg, such as from about 0.20 to about 2.00, such as from about 0.50 to about 1.50 mg,

In certain embodiments, the tissue product may comprise a single homogeneous or blended layer, or may be formed from one or more basesheets, which may be multi-layered. When the basesheet is multi-layered, it may include two, three or more layers. For example, the basesheet may include three layers, such as first and second outer layers and an intermediate layer disposed therebetween. The layers may include the same or different fiber types. For example, the first and second outer layers may comprise short, low roughness wood pulp fibers, such as hardwood kraft pulp fibers, and the middle layer may include long, low roughness wood pulp fibers, such as northern softwood kraft pulp fibers. may include

If the web comprises multiple layers, the relative weight percentage of each layer may vary. For example, the web may include first and second outer layers and an intermediate layer, wherein the first outer layer comprises from about 25 to about 35 weight percent of the layered web, and the intermediate layer is from about 30 to about 50 weight percent of the layered web. weight percent, and the second outer layer comprises from about 25 to about 35 weight percent of the layered web.

The multilayer basesheet useful in the present invention may be formed using any number of different processes known in the art, such as the process disclosed in U.S. Patent No. 5,129,988, the content of which is herein incorporated in a manner consistent with this disclosure. is used One process for forming a multilayer basesheet is shown in FIG. 1 . A dilute aqueous suspension of papermaking fibers is dispersed from a headbox 10 having an upper headbox wall 12 and a lower headbox wall 14 and first and second dividers 16 , 18 . In this way, the headbox may be used to form a base sheet having an outer layer 22 , 24 and an intermediate layer 20 , wherein each layer may include the same or different papermaking fibers.

An endless running forming fabric 26 , suitably supported and driven by rolls 28 , 30 to form the multi-layer basesheet, receives the layered paper stock being issued at the headbox 10 . Once retained on the fabric 26 , the layered fiber suspension transmits water through the fabric as indicated by arrow 32 . Water removal is achieved by a combination of gravity, centrifugal force and vacuum suction, depending on the configuration being molded.

In certain embodiments, one or more layers of a multilayer basesheet, such as an interlayer, may be formed without significant amounts of internal fiber-to-fiber bond strength. In this regard, the fibrous furnish used to form the desired layer may be treated with a chemical debonding agent. The debonding agent may be added to the fiber slurry during the pulping process or it may be added directly to the fiber slurry prior to the headbox. Suitable debonding agents that may be used in the present invention include cationic debonding agents, particularly quaternary ammonium compounds, mixtures of polyhydroxy compounds with quaternary ammonium compounds, and modified polysiloxanes.

Suitable cationic deconjugating agents include, for example, fatty acid dialkyl quaternary amine salts, mono fatty acid alkyl tertiary amine salts, primary amine salts, imidazoline quaternary salts, and unsaturated fatty acid alkyl amine salts. Other suitable debonding agents are described in US Pat. No. 5,529,665, the contents of which are incorporated herein in a manner consistent with the present invention. In one embodiment, the debonding agent used in the process of the present invention is an organic quaternary ammonium chloride, such as those available under the trade designation ProSoft™ (Solenis, Wilmington, Del.). The debonding agent may be added to the fiber slurry in an amount from about 1.0 kg per metric ton to about 15 kg per metric ton of fibers present in the slurry.

Particularly useful quaternary ammonium debonding agents are imidazoline quaternary ammonium debonding agents such as oleyl-imidazoline quaternary, dialkyl dimethyl quaternary debonding agents, ester quaternary debonding agents, diamidoamine quaternary debonding agents. binders and the like. The imidazoline-based debonding agent may be added in an amount of 1.0 to about 10 kg/MT.

In other embodiments, a layer or other portion of the basesheet, including the entire basesheet, may optionally include a wet or dry toughening agent. As used herein, “wet strength agents” are materials used to secure bonds between fibers in a wet state. Any material that, when added to an effective level to a tissue web, provides the basesheet with a wet geometric tensile strength:dry geometric tensile strength ratio of greater than 0.1 may be referred to as a wet toughening agent for the purposes of this invention. A particularly preferred wet galvanizing agent is a temporary wet galvanizing agent. As used herein, "temporary wet strength agents" are those that show less than 50% of their original wet strength after being saturated with water for 5 minutes.

Suitable temporary wet modifiers include materials capable of reacting with hydroxyl groups, such as cellulosic pulp fibers, to form reversible hemiacetal bonds in the presence of excess water. Suitable temporary wet forcing agents are known to those skilled in the art. Non-limiting examples of suitable temporary wet modifiers for the fibrous structure of the present invention include glyoxalated polyacrylamide polymers, such as cationic glyoxalated polyacrylamide polymers. Temporary wet strength agents useful in the present invention may have an average molecular weight of from about 20,000 to about 400,000, such as from about 50,000 to about 400,000, such as from about 70,000 to about 400,000, such as from about 70,000 to about 300,000, such as from about 100,000 to about 200,000. In certain cases, the temporary wet strength agent is a commercially available temporary wet strength agent such as those sold under the trade names Hercobond™ (Solenis, Wilmington, DE) or FennoBond™ (Kemira Chemicals, Inc., Atlanta, Georgia). may include

In other cases, the basesheet may optionally include dry strength additives such as carboxymethyl cellulose resins, starch-based resins, and mixtures thereof. Particularly preferred dry strength additives are cationic starches and mixtures of cationic and anionic starches. In certain instances, the dry coagulant is a commercially available modified starch such as those sold under the trade name RediBOND™ (Ingredion, Westchester, IL) or such as those sold under the trade name Aqualon™ (Ashland LLC, Bridgewater, NJ). commercially available carboxymethyl cellulose resins.

The amount of wet coarse or dry coarse strength added to the pulp fibers is at least about 0.1 dry weight percent based on the dry weight of the fibers, more specifically about 0.2 dry weight percent or more, and still more specifically about 0.1 to about 3 dry weight percent dry weight percent. may be

Tissue basesheets useful for forming the tissue products of the present invention may be formed using any of several well-known manufacturing processes. For example, in certain embodiments, the tissue product may be manufactured by an through-air drying (TAD) manufacturing process, an Advanced Tissue Forming System (ATMOS) manufacturing process, a Structured Tissue Technology (STT) manufacturing process, a conventional wet pressing (“CTEC”) manufacturing process. (also referred to as ) manufacturing process or belt creped manufacturing process. In particularly preferred embodiments, the tissue product is manufactured by a creping through air drying (CTAD) process or an uncreping through air drying (UCTAD) process.

Referring now to FIG. 2 , a method of making a breathable dry paper sheet is illustrated. Shown is a twin wire former having a papermaking headbox 34, such as a multilayer headbox, that injects or deposits a stream 36 of an aqueous suspension of papermaking fibers onto a forming fabric 38 positioned on a forming roll 39. has been The forming fabric functions to support and downstream convey the newly formed wet web in the process when the web is partially dewatered to a consistency of about 10 dry weight percent. While the wet web is supported by the forming fabric, further dewatering of the wet web may be effected, for example by vacuum suction.

The wet web is then transferred from the forming fabric to the transfer fabric 40 . In one embodiment, the transfer fabric may run at a slower speed than the forming fabric to impart increased stretch to the web. This is commonly referred to as a "rush" warrior. The relative speed difference between the two fabrics may be 0-60%, more specifically about 15-45%. The transfer is preferably performed with the aid of the vacuum shoe 42 so that the forming fabric and the transfer fabric converge and diverge simultaneously at the leading edge of the vacuum slot.

The web is then transferred from the transfer fabric to the breathable drying fabric 44 with the aid of a vacuum transfer roll 46 or vacuum transfer shoe, optionally again using a fixed gap transfer as described above. The air-drying fabric may travel at approximately the same or a different rate relative to the transfer fabric. If necessary, the breathable drying fabric can be moved at a slower rate to further improve stretchability. The transfer can be effected with vacuum assistance to ensure the deformation of the sheet conforming to the breathable drying fabric, thus resulting in the desired bulk and imparting the web with a three-dimensional topographical pattern. Suitable breathable drying fabrics are described, for example, in US Pat. Nos. 6,998,024, 7,611,607, and 10,161,084, the contents of which are incorporated herein by reference in a manner consistent with the present invention.

In one embodiment, the breathable dry fabric comprises a single layer fabric woven from weft and warp filaments. In certain instances, the weft filaments may include two or more different diameters and may be interwoven with the warp filaments to form a textured sheet contacting surface having substantially continuous machine direction ripples separated by valleys. In other instances, the woven fabric may include a plurality of substantially continuous machine direction ripples formed from a plurality of warp strands grouped together and supported by a plurality of weft strands of two or more diameters. During drying, the web can be macroscopically arranged to form a textured three-dimensional surface that conforms to the surface of the air-dried fabric.

The side of the web in contact with the air-drying fabric is commonly referred to as the "fabric side" of the paper web. As described above, the fabric side of the paper web may have a shape that conforms to the surface of the air-dried fabric after the fabric is dried in the air-dried fabric. On the other hand, the opposite side of the paper web is commonly referred to as the "air side".

The level of vacuum used for web transfer may be from about 3 to about 15 inches of mercury (75 to about 380 mm of mercury), preferably about 5 inches (125 mm) of mercury. The vacuum shoe (negative pressure) is created by the use of positive pressure from the opposite side of the web to blow the web onto the next fabric, in addition to or instead of sucking the web onto the next fabric by vacuum. may be supplemented or replaced. Also, a vacuum roll or rolls may be used to replace the vacuum shoe(s).

The web, while supported by the air-drying fabric, is dried by the air-drying machine 48 to a consistency of at least about 94% and then transferred to the carrier fabric 50 . The dried basesheet 52 is transferred to a reel 54 using a carrier fabric 50 and an optional carrier fabric 56 . A pressurized turning roll 58 may optionally be used to facilitate transfer of the web from the carrier fabric 50 to the fabric 56 .

In one embodiment, the reel 54 shown in FIG. 2 may operate at a slower speed than the fabric 56 in the rapid transfer process for building bulk into the paper web 52 . For example, the relative speed difference between the reel and the fabric may be from about 5% to about 25%, particularly from about 12% to about 14%. Rapid transfer on the reel can occur alone or with a rapid transfer process upstream, such as between a forming fabric and a transfer fabric.

Once the web is formed, a binder composition is applied to at least one side of the web. In this way, the present invention provides a tissue product comprising a web having first and second outer surfaces, wherein at least one outer surface comprises a topically applied binder, in particular a binder applied in a network. As used herein, the term “network” is used to describe any binder pattern that serves to bond the sheets together. The pattern may be regular or irregular, and may be continuous or discontinuous.

Referring now to FIG. 3 , one embodiment of applying a binder material to one outer surface of a web is shown. A paper web 52 is shown passing through a binder material application station 65 . Station 65 includes a transfer roll 67 in contact with a rotogravure roll 68 in communication with a reservoir 69 containing a suitable binder 70 . Although gravure printing of the binder is shown, other means of applying the binder material may also be used, such as digital printing methods such as foam application, spray application, flexographic printing, or inkjet printing. Rotogravure roll 68 applies binder material 70 to one side of web 52 in a preselected pattern.

4-6 show several different printing patterns that can be used to apply a binder material to a basesheet according to the present invention. As shown in Figure 4, the pattern may include a series of discontinuous dots. In one embodiment, for example, the dots may be spaced apart such that there are from about 25 to about 35 dots per inch (25.4 mm) in the machine direction and/or cross-machine direction. The dots may have a diameter of, for example, from about 0.01 inches (0.25 mm) to about 0.03 inches (0.76 mm). In one particular embodiment, the dots may have a diameter of about 0.02 inches (0.51 mm), and there may be approximately 28 dots per inch (25.4 mm) in a pattern extending in both the machine direction and the cross machine direction. In addition to dots, various other individual shapes such as elongated ovals or rectangles may also be used when printing the binder material on the sheet.

Figure 5 shows a print pattern in which the binder material print pattern is constructed from a number of individual adherends, each consisting of three elongated hexagons. In one embodiment, each hexagon may be about 0.02 inches (0.51 mm) long and may have a width of about 0.006 inches (0.15 mm). Approximately 35 to 40 deposits per inch (25.4 mm) can be spaced apart in the machine and cross machine directions.

6 shows an alternative binder material pattern in which the binder material is printed in a reticulated pattern on a sheet. The dimensions are similar to those of the dot pattern of FIG. 4 . A reticulated pattern, providing a continuous network of binder material, may result in relatively greater sheet strength than a similar pattern of discontinuous elements, such as the dot pattern of FIG. 4 . It will be appreciated that, in addition to those shown above, many other patterns may be used depending on the desired properties of the final product.

Referring again to FIG. 3 , after the binder material 70 has been applied, the sheet 52 is attached to the heated creping cylinder 75 by a pressure roll 76 . The sheet 52 is conveyed a certain distance on the surface of the heated creping cylinder 75 and then removed therefrom by the action of the creping blade 78 . The creping blade 78 performs a controlled pattern creping operation on the side of the sheet 52 to which the binder material 70 is applied.

Once creped, the sheet 52 is pulled through an optional drying station 80 . The drying station may include any type of heating unit, such as an oven powered by infrared heat, microwave energy, hot air, and the like. Alternatively, the drying station may include photocuring, UV-curing, corona discharge treatment, electron beam curing, curing with a reactive gas, aeration heating or impinging jet heating, infrared heating, contact heating, induction heating, microwave or RF heating. Other drying methods, such as curing with heated air, may be included. However, depending on the binder material selected, the drying station 80 may not be necessary. After passing through the drying station 80, the sheet 52 may be wound into a roll 85 of material or product.

In certain instances, the binder composition may be selected to aid in creping of the web, as well as improve one or more physical properties of the web, such as, for example, dry strength, wet strength, stretch and tear resistance. Certain binder compositions that may be used in the present invention include latex compositions. The latex composition may include a non-carboxylated latex emulsion or a carboxyl-functional latex emulsion polymer. Non-carboxylated latex emulsions useful in the present invention may comprise aqueous polymer dispersions of vinyl acetate and ethylene. Suitable non-carboxylated latex emulsions include vinyl acetate and ethylene emulsions such as Vinnapas™ EZ123 commercially available from Wacker Polymers, LP, Allentown, PA. In other instances, the binder composition may include a carboxyl-functional latex polymer, such as Vinnapas™ EP1133, commercially available from Wacker Polymers, LP, Allentown, PA.

Latex polymers useful in the present invention may include unsaturated monomers such as vinyl acetate and ethylene monomers and may be polymerized in the presence of surfactants and initiators to produce emulsion polymerized polymer particles. Unsaturated monomers include carbon-carbon double bond unsaturation and generally include vinyl monomers, styrene monomers, acrylic monomers, allyl monomers, acrylamide monomers, as well as carboxyl functional monomers. Vinyl monomers include vinyl esters such as vinyl acetate, vinyl propionate and similar vinyl lower alkyl esters, vinyl halides, vinyl aromatic hydrocarbons such as styrene and substituted styrenes, vinyl aliphatic monomers such as alpha olefins and conjugated dienes, and vinyl alkyls. ethers such as methyl vinyl ether and similar vinyl lower alkyl ethers. Acrylic monomers include aromatic derivatives of acrylic and methacrylic acid as well as lower alkyl esters of acrylic or methacrylic acid having an alkyl ester chain of 1 to 12 carbon atoms. Useful acrylic monomers include, for example, methyl, ethyl, butyl, and propyl acrylates and methacrylates, 2-ethyl hexyl acrylate and methacrylates, cyclohexyl, decyl, and isodecyl acrylates and methacrylates, and various similar acrylates and methacrylates.

In certain embodiments, the latex polymer may comprise a carboxyl-functional latex polymer comprising copolymerized carboxyl-functional monomers such as acrylic acid and methacrylic acid, fumaric acid or maleic acid or similar unsaturated dicarboxylic acids, , wherein preferred carboxyl monomers are acrylic acid and methacrylic acid. In certain instances, the carboxyl-functional latex polymer may comprise from about 1 to about 50% copolymerized carboxyl monomer, the balance being other copolymerized ethylene monomers. Suitable carboxyl-functional latex polymers include carboxylated vinyl acetate-ethylene polymer emulsions, such as Vinnapas® EP1133, commercially available from Wacker Polymers, LP (Allentown, PA).

In certain instances, the binder composition may optionally contain an anti-blocking additive designed to modify the surface chemistry or properties of the binder film on the basesheet. Suitable anti-blocking additives generally do not react chemically with binders and may include: 1) surfactants such as sodium of stearic acid, palmitic acid, oleic acid, lauric acid and tall oil fatty acids and anionic surfactants such as potassium salts, and nonionic surfactants such as polyoxyethylene glycol reacted with a lyophilic compound; 2) non-reactive additives such as silicones, waxes, oils designed to modify the surface chemistry of at least one outer surface of the web to reduce blocking; and 3) soluble or insoluble crystals, such as sugars, talc, clay, etc., designed to reduce the tendency to reside on the surface of the binder film and cause blockage to adjacent web surfaces. The amount of anti-blocking additive in the binder composition relative to the amount of carboxyl-functional latex emulsion polymer on a weight percent solids basis is about 1 to about 25%, more specifically about 5 to about 20%, more specifically about 10 to about It can be 15%.

Accordingly, in certain embodiments, binders useful in the present invention are formulated with essentially non-crosslinked latex polymers, such as vinyl acetate-ethylene latex polymers, and optionally polysaccharides, to prevent blocking upon drying of the tissue web. the same anti-blocking agent.

In certain preferred embodiments, polyfunctional aldehydes such as glyoxalated polyacrylamide and glyoxal, and polyamide-epichlorohydrin (PAE) resins and polyamide-polyamine-epichlorohydrin (PPE) resins are combined with It may be desirable to form the tissue article of the present invention using a binder that is substantially free of the same azetidinium-functional crosslinking polymer. Thus, in a preferred embodiment, the latex polymer, which may include either non-carboxylated or carboxylated latex polymer, is not crosslinked before or after application to the tissue web.

In certain instances, the binder composition may be applied to the base web in a preselected pattern. In one embodiment, for example, the binder composition can be applied to the web in a reticulated pattern such that the patterns are interconnected to form a net-like design or grid on the surface. In other embodiments, the binder composition may be applied to the web in a pattern exhibiting a series of discontinuous shapes. For example, the binder composition may be applied in a pattern of discrete dots. Despite being composed of discrete shapes, these patterns provide the desired physical properties without covering a significant portion of the surface area of the web.

In certain preferred embodiments, the binder composition is applied to only one side of the web to cover from about 15 to about 75% of the surface area of the web. More specifically, for most applications, the binder composition will cover from about 20% to about 60% of the surface area of the web. The total amount of binder composition applied to the web may range from about 1 to about 25 weight percent, such as from about 2 to about 10 weight percent, based on the total weight of the web.

3 , only one side of the web is treated and the binder composition is left on the untreated side. Leaving one side of the tissue web untreated can provide a variety of advantages and advantages in some cases. For example, untreated cotton can increase the ability of the tissue web to absorb liquids more quickly. In addition, the untreated cotton may have a greater texture than if the cotton was treated with the binder composition.

Furthermore, the process shown in FIG. 3 represents only one possible method for applying the binder composition to a web. Other methods of application may be suitable for applying the binder composition to the web. For example, a variety of printing methods may be used to print the binder composition on a web depending on the particular field of application. Such printing methods may include direct gravure printing, offset gravure printing, or flexographic printing.

As noted above, in addition to having a binder composition applied to one or more exterior surfaces, the tissue product may undergo further transformations such as calendering, treatment with a softening composition, embossing, slitting, winding and/or folding.

In certain embodiments, a tissue product of the present invention may be treated with an emollient composition to improve tactile feel or deliver a benefit to the end user. As used herein, the term “emollient composition” refers to any chemical composition that improves the perceived tactile sensation of an end user holding a particular tissue product and rubbing it across the skin. Suitable emollient compositions include, for example, basic waxes such as paraffin and beeswax and petrolatum, as well as oils such as mineral and silicone oils, quaternary ammonium compounds having long alkyl chains, functional silicones, fatty acids, fatty alcohols and fatty esters; more complex lubricants and emollients such as

Thus, in one embodiment, the tissue product of the present invention comprises one or more oils such as mineral oil, a wax such as paraffin, or a plant extract such as chamomile and aloe vera, as disclosed in US Pat. Nos. 5,885,697 and 5,525,345. emollient composition, the contents of which are incorporated herein in a manner consistent with the present invention.

In other embodiments, the tissue product is an emollient composition comprising a polysiloxane, more preferably a composition comprising an amino-functional polysiloxane, a surfactant and optionally a skin conditioning agent, such as the composition disclosed in US Patent Publication No. 2006/0130989. processed, the contents of which are incorporated herein in a manner consistent with the present invention. In certain preferred embodiments, the polysiloxane is an amino-functional polysiloxane, the surfactant is an ethoxylated alcohol or an ethoxylated propoxylated alcohol, and the skin conditioning agent is vitamin E and/or aloe vera.

In still other embodiments, the tissue product may be treated with an emollient composition comprising a cationic emollient compound and a relatively high molecular weight polyhydroxy compound. Suitable cationic softening compounds are all, for example, amidoamine quaternary ammonium compounds, diamidoamine quaternary ammonium compounds, ester quaternary ammonium compounds, alkoxy alkyl quaternary ammonium compounds, benzyl quaternary ammonium compounds, alkyl quaternary quaternary ammonium compounds including ammonium compounds and imidazolinium compounds. Examples of polyhydroxy compounds useful in the present invention include at least about 1,000 g/mole, more preferably greater than about 2,000 g/mole, even more preferably greater than about 4,000 g/mole, more preferably greater than about 6,000 g/mole, Examples include, but are not limited to, polyethylene glycol and polypropylene glycol having a molecular weight of from about 1,000 to about 12,000 g/mole, more preferably from about 4,000 to about 10,000 g/mole, and even more preferably from about 6,000 to about 8,000 g/mole. doesn't happen

In another embodiment, the emollient composition may include a cationic emollient compound, a relatively high molecular weight polyhydroxy compound, and a polysiloxane. Any polysiloxane capable of enhancing the tactile softness of the tissue sheet can be formed into a gel, precipitate or, when mixed, which precludes application to the tissue sheet when solutions or emulsions of cationic emollients, polyhydroxy and silicone are compatible. It is suitable for incorporation in this manner, as long as it does not form other physical defects.

In other embodiments, the emollient compositions useful in the present invention comprise essentially water, a cationic emollient compound such as a quaternary ammonium compound, a polyhydroxy compound having a molecular weight of at least about 1,000 g/mole, and optionally silicone or glycerin, or may be composed of mixtures thereof. In other embodiments, the emollient composition may consist essentially of water, a quaternary ammonium compound, a polyhydroxy compound having a molecular weight of at least about 1,000 g/mole, silicone, and glycerin. When incorporated into an emollient composition, the amount of glycerin in the emollient composition may be from about 5.0 to about 40 weight percent, more particularly from about 10 to about 30 weight percent, even more particularly from about 15 to about 20 weight percent.

All of the aforementioned emollient compositions may optionally contain beneficial agents, such as skin conditioning agents or humectants, which may be provided in amounts ranging from about 0.01 to about 5% by weight of the composition. Suitable wetting agents include lactic acid and its salts, sugars, ethoxylated glycerin, ethoxylated lanolin, corn syrup, hydrolyzed starch hydrolysates, urea and sorbitol. Suitable skin conditioning agents include allantoin, kaolin, zinc oxide, aloe vera, vitamin E, petrolatum and lanolin. Again, the aforementioned additives are generally complementary to the softening compositions of the present invention and generally do not significantly adversely affect important tissue product properties, such as the strength or absorbency of the tissue product, or the softening provided by the softening compositions of the present invention. does not negatively affect

The softening composition is generally applied to a creped tissue web having a binder composition disposed on one or two outermost surfaces, more preferably at least one outer surface, of the dry tissue web. The method by which the softening composition is applied to the tissue sheet may be accomplished by any method known in the art. For example, in one embodiment, the composition may be applied by a contact printing method such as gravure, offset gravure, flexographic printing, or the like. Contact printing methods often allow for topical application of the composition to a tissue sheet. In other embodiments the softening composition may be applied to the tissue web by a non-contact printing method, such as inkjet printing, digital printing of any kind, and the like.

In certain preferred embodiments the softening composition is prepared as an aqueous solution and may be applied to the web by spraying or rotogravure printing. In this way, it is believed that the tactile softness of the tissue sheet and the resulting tissue product can be improved due to the presence of a softening composition on the surface of the tissue product. When applied as an aqueous solution, the emollient composition may comprise from about 50 to about 90%, more preferably from about 60 to about 80% water by weight of the composition.

In other cases, the basesheet prepared as described above may be embossed and overlaid to produce the tissue product of the present invention. For example, a tissue product of the present invention may be provided as a multi-ply product comprising two or more plies, such as two, three or four plies, wherein the plies are embossed and laminated together. In one embodiment, the multi-ply article of the present invention may be made using an embossing lamination apparatus, such as described in US Pat. Nos. 3,556,907, 3,867,225, and 5,339,730, the contents of which are consistent with this disclosure. is incorporated herein by reference. For example, the two plies may be embossed separately, respectively, between the embossing roller and the counter roller or pressure roller. The two plies may then be brought into a face-to-face relationship with each other and joined such that the protrusions of one ply are seated between the protrusions of the other ply. Typically, lamination of two plies is obtained between one of the embossing rollers and the lamination roller, while the two embossing rollers are not in contact.

Test Methods

basis weight

Prior to testing, all samples are conditioned under TAPPI conditions (23°C and 50°C 2% relative humidity) for a minimum of 4 hours. The basis weight of a sample is determined by selecting 12 products (also called sheets) of the sample and making two stacks of 6 sheets. If the sample consists of a perforated sheet of bathroom or towel tissue, the perforations should be aligned on the same side when stacking the usable units. Using a precision cutter, cut each stack into exactly 10.16 Х 10.16 cm (4.0 Х 4.0 in) squares. The two stacks of cut squares are combined to make a basis weight pad of 12 squares thick. The basis weight pad is then weighed on the top loading balance with a minimum resolution of 0.01 g. The top loading balance must be protected from air drafts and other disturbances using draft shields. Record the weight when the reading of the upper loading balance is constant. The mass (grams) of the sample per unit area (square meter) is calculated and reported as the basis weight with units of grams per square meter (gsm).

caliper

Caliper is measured according to TAPPI Test Method Test Method T 580 pm-12 "Thickness (Caliper) of Towels, Tissues, Napkins and Beauty Products". The micrometer used to perform caliper measurements is an Emveco 200-A tissue caliper tester (Emveco, Inc., Newburgh, OR). The micrometer has a load of 2 kPa, a ^{pressure foot area of 2,500 mm 2} , a pressure foot diameter of 56.42 mm, a duration of 3 seconds, and a descent rate of 0.8 mm/s.

Slough

The slough test provides a quantitative measure of the abrasion resistance of a tissue sample. More specifically, this test measures the resistance of a material to abrasive action when the material is exposed to a horizontally reciprocating surface abrasive. The equipment used to measure the slough is similar to that described in US Pat. No. 6,808,595, the disclosure of which is incorporated herein by reference in a manner consistent with the present invention. The abrasive spindle consists of a stainless steel rod approximately 1.25 cm (0.495 inches) in diameter and 15.25 cm (6 inches) long. The abrasive portion of the abrasive spindle is 10.8 cm (4.25 inches) long and consists of an 18/22 abrasive coating (commercially available from Superabrasives, Inc., Wixom, MI) applied around the entire perimeter of the abrasive spindle. . The abrasive spindle is mounted perpendicular to the face of the machine such that the abrasive portion of the abrasive spindle extends the entire distance from the face of the machine. On each side of the abrasive spindle, a pair of clamps are positioned, one movable and the other fixed. The clamps are 4 inches (10 cm) apart and centered relative to the grinding spindle. The movable clamp (weight approximately 21 grams) can slide freely in the vertical direction, and the weight of the movable clamp provides a means to ensure that the tension of the tissue sheet sample across the surface of the abrasive spindle is constant. An instrument for measuring slough according to the present invention is available from Accelerated Analytical Laboratories, Milwaukee, Wisconsin.

Before the test, any loose dust shall be removed from the grinding spindle with compressed air. If other debris is present on the grinding spindle, the spindle can be washed with warm water and dishwashing liquid, rinsed with distilled water, and dried in the oven. If the abrasive spindle is cleaned prior to use, care should be taken to rinse all cleaning liquid from the abrasive spindle and allow it to dry thoroughly before use.

Prior to testing, samples are conditioned under TAPPI conditions (23°C and 50°2% relative humidity) for a minimum of 4 hours. For perforated bathroom tissue products, the samples are prepared by first stretching the tissue and separating it into three sheets of length. Using a precision cutter such as a JDC-3 cutter (commercially available from Thwing-Albert Instrument Company, Philadelphia, Pa.), each sample was cut into 7.0 ± 0.5 inches (177.8 ± 13 mm) in the machine direction (MD) and Cut to a size of 76.2 ± 1 mm (3.0 ± 0.04 inches) in the cross machine direction (CD). 7 , when cutting a perforated bathroom tissue product, the sample 100 has a first end 102 extending 1 inch (25.4 mm) past the first line of perforation 105 and a second end 104 is cut to extend 2 inches (50.8 mm) past second line of perforation 107 to ensure that the spindle does not wear across lines of perforation 105 , 107 in sample 100 .

When testing rolled and perforated bathroom tissue products, the test shall be performed on the outer surface of the roll as it unwinds. In general, rolled and perforated bathroom tissue products are not separated into individual plies prior to testing, but the outer surface of the product is tested as it is unwound from the roll. When testing a folded cosmetic tissue product, the product is separated into individual plies and the outer facing side of one of the outer plies is tested.

Each tissue sample weighs close to 0.1 mg. One end of the tissue sheet sample is clamped in a stationary clamp, after which the sample is loosely draped against an abrasive spindle and clamped in a sliding clamp. The entire width of the sample should be in contact with the abrasive spindle. The sliding clamp can then drop to provide a constant tension across the abrasive spindle. The entire width of the tissue sheet sample should be in contact with the abrasive spindle.

Once the sample is fixed, the test is initiated by moving the polishing spindle back and forth at an angle of approximately 15 degrees from the centered vertical centerline in reciprocating horizontal motion relative to the tissue sample for 40 cycles at a rate of 73.5 ± 0.5 cycles per minute. Depending on the spindle cycle, the spindle also rotates counterclockwise (as viewed from the front of the machine) at a speed of about 5 RPM. Once the 40 cycles are complete, the tissue sample is removed from the bath with a fingertip and blown over both sides of the sample with air having a flow rate of approximately 3.4 scfm for approximately 13 seconds to remove debris.

The tissue sheet sample is then weighed close to 0.1 mg and the weight loss is calculated. The difference between the initial weight and the post-test weight is the amount of slaw. Ten samples are tested and the average weight loss value in milligrams (mg), the slough value for the sample, is recorded.

Bursting strength (wet or dry)

Burst strength is measured using an EJA Burst Tester (Series # 50360, commercially available from Thwing-Albert Instrument Company, Philadelphia, PA). The test procedure is in accordance with TAPPI T570pm-00 except for the test speed. The test specimen is clamped between two concentric rings whose inner diameter defines a circular area under test. A tub assembly, which is a smooth spherical steel ball on top, is positioned perpendicular to and centered below the rings holding the test specimen. Raise the pass assembly 6 inches per minute so that the steel ball makes contact with the test specimen and eventually passes through the test specimen to the specimen breaking point. The maximum force applied by the assembly through the moment of failure of the specimen is reported as the burst strength in grams force (gf) of that specimen.

The pass assembly consists of a spherical pass member, a stainless steel ball having a diameter of 0.625 ± 0.002 inches (15.88 ± 0.05 mm), spherically finished to 0.00004 inches (0.001 mm). A spherical pass member is permanently fixed to the end of a 0.375 ± 0.010 inch (9.525 ± 0.254 mm) solid steel bar. A 2000 g load cell is used and 50% of the load range is selected, ie 0 to 1000 g. The travel of the probe is such that the top surface of the spherical ball reaches a distance of 1.375 inches (34.9 mm) above the plane of the clamped sample under test. The means for holding the test specimen for testing, consisting of upper and lower concentric rings of about 0.25 inch (6.4 mm) thick aluminum, held between the samples by pneumatic clamps were operated under a source of filtered air at 60 psi. The clamping rings have an inner diameter of 3.50 ± 0.01 inches (88.9 ± 0.3 mm) and an outer diameter of approximately 6.5 inches (165 mm). The clamping faces of the clamping rings are coated with commercial grade neoprene about 0.0625 inches (1.6 mm) thick with a Shore hardness of 70 to 85 (A scale). Neoprene does not need to cover the entire surface of the clamping ring but matches the inner diameter, so it has an inner diameter of 3.50±0.01 inches (88.9±0.3 mm), a width of 0.5 inches (12.7 mm), and thus an outer diameter of 4.5±0.01 inches (88.9±0.3 mm). 0.01 inches (114±0.3 mm). For each test, a total of three sheets of product are combined.

The sheets are stacked on top of each other in such a way that the machine direction of the sheets is aligned. If the samples contain multiple plies, the plies are not separated for testing. In each case, the test sample comprises three sheets of product. For example, if the product is a two-ply tissue product, three sheets of the product are tested, for a total of 6 layers. If the product is a single ply tissue product, 3 sheets of product, i.e. a total of 3 ply, are tested.

Samples are conditioned under TAPPI conditions for a minimum of 4 hours and cut into 127 Х 127 ± 5 mm squares. For wet rupture measurements, after conditioning, samples were wetted for testing with 0.5 mL of deionized water dispensed with an automated pipette. Wet samples are tested immediately after defecation.

The peak load (gf) and energy versus peak (g-cm) were recorded, and the process was repeated for all remaining specimens. A minimum of 5 specimens are tested per sample, and the average peak load of the 5 tests is reported.

tear

The tear test was performed according to TAPPI test method T-414 "Internal Tearing Resistance of Paper (Elmendorf-type method)" using a falling pendulum apparatus such as Lorentzen & Wettre Model SE 009. Tear strength is directional, and MD and CD tear are measured independently.

More specifically, take a rectangular test specimen of the sample to be tested, with the test specimen measuring 63° 0.15 mm (2.5° 0.006 inches) in the direction to be tested (such as in the MD or CD direction) and 73 to 114 mm (2.9 inches) in the other direction. to 4.6 inches) from the tissue product or tissue basesheet. The specimen edges shall be cut parallel and perpendicular to the test direction (non-skewed). Any suitable cutting device capable of having the specified precision and accuracy may be used. Specimens shall be taken from sample areas free of folds, creases, crimp lines, perforations, or any other distortion that makes the specimen unusually different from the rest of the material.

The number of plies or sheets to be tested is based on the number of plies or sheets required for the test result to fall between 20 and 80% on the linear range scale of the tear tester, more preferably between 20 and 60% on the linear range scale of the tear tester. is determined by The sample should preferably be cut at least 6 mm (0.25 inch) from the edge of the material from which the specimen is to be cut. When more than one sheet or ply is required for the test, the sheets are placed facing the same direction.

The specimen is then placed between the clamps of the falling pendulum device and the edge of the specimen is aligned with the front edge of the clamp. Close the clamps and cut a 20 mm slit to the tip of the specimen with a cutting knife usually attached to the machine. In the Lorentzen & Wettre Model SE 009, for example, the slit is created by pushing the cutting knife lever down until the stop is reached. The slit should be clean and free from tears or blemishes as this slit will function to initiate tearing during subsequent testing.

The pendulum is released and the tear value, which is the force required to completely tear the specimen, is recorded. The test is repeated a total of 10 times for each sample, and the average of the 10 readings is reported as the tear strength. Tear strength is reported in grams of force (gf). The average tear value is the tear strength for the direction tested (MD or CD). "Geometric mean tear strength" is the square root of the product of the average MD tear strength and the average CD tear strength. Lorentzen & Wettre Model SE 009 has a setting for the number of plies tested. In some testing machines, it may be necessary to multiply a factor by the reported tear strength to give the tear strength per ply. For basesheets intended to be multi-ply products, tear results are reported as tearing of the multi-ply product rather than single-ply basesheets. This is done by multiplying the single-ply basesheet tear value by the number of plies in the finished product. Similarly, multi-ply finished product data for tear is presented as tear strength for finished sheets rather than individual ply. Calculations can be made using various means, but in general this will be done by entering the number of sheets to be tested rather than the number of plies to be tested into the measuring device. For example, two sheets are two single-ply sheets for a one-ply product and two two-ply (four-ply) sheets for a two-ply product.

Seal

Tensile testing is performed on a tensile testing machine that maintains a constant elongation, and each specimen tested is 3 inches wide. Tests are performed under TAPPI conditions. Prior to testing, samples were conditioned under TAPPI conditions (23 ± 1 °C and 50 ± 2% relative humidity) for at least 4 hours before being sampled in a JDC Precision Sample Cutter (Model No. JDC 3-10, Thwing-Albert Instrument Company, Philadelphia, PA). , serial No. 37333) or equivalent was cut into strips 3±0.05 inches (76.2±1.3 mm) wide in machine direction (MD) or cross machine direction (CD) orientation. The instrument used to measure the tensile strength was MTS Systems Sintech 11S, serial No. It was 6233. The data acquisition software was MTS Testworks® (MTS Systems Corp., Research Friangle Park, NC) for Windows version 3.10. Depending on the strength of the sample under test, the load cell was selected either 50N or up to 100N, with most of the peak load values falling between 10 and 90% of the full scale value of the load cell. The gauge length between the jaws was 4±0.04 inches (101.6±1 mm) for cosmetic wipes and towels and 2±0.02 inches (50.8±0.5 mm) for bathroom wipes. The crosshead speed was 10±0.4 inches/min (254±1 mm/min) and the breaking sensitivity was set at 65%. Samples were placed in the jaws of the instrument centered both vertically and horizontally. The test was then started and the test ended when the specimen broke. The peak load was reported as the "MD tensile strength" or "CD tensile strength" of the specimen depending on the orientation of the sample under test. Ten representative specimens were tested for each product or sheet, and the arithmetic mean of all individual specimen tests was reported as the appropriate MD or CD tensile strength in grams per 3 inches (g/3"). Tensile Tester Calculate Tensile energy absorbed (TEA) and slope. TEA is ^{reported in units of g cm/cm 2} , and slope is recorded in units of kilograms (kg). Both TEA and slope depend on the direction. , and thus measure the MD and CD directions independently.

All products were tested in product form without being separated into individual plys. For example, a two-ply product was tested as two-ply and recorded as such. When measuring the tensile properties of the basesheet, the number of plies used was dependent on the intended end use. For example, if the basesheet was intended for use in a two-ply product, a combination of two-ply basesheets was tested.

surface smoothness

Surface smoothness was measured using an EMTEC Tissue Softness Analyzer (“TSA”) (Emtec Electronic GmbH, Leipzig, Germany). The TSA contains a rotor with vertical blades that rotate on a tissue sample by applying a defined contact pressure. The blade is pressed against the sample with a 100 mN load, and the rotational speed of the blade is 2 revolutions per second. The contact between the vertical blade and the tissue sample creates a vibration that is sensed by the vibration sensor. The sensor sends a signal to the PC for processing and display. The signal is represented as a frequency spectrum. The frequency spectrum is analyzed by the relevant TSA software to determine the amplitude of frequency peaks occurring in the range of 200 to 1000 Hz. This peak is commonly referred to as the TS750 value ( ^{in units of dB V 2} rms) and represents the surface smoothness of the tissue sample. High amplitude peaks correlate with rougher surfaces, while low amplitude peaks correlate with smoother surfaces.

A tissue product sample was prepared by cutting a circular sample having a diameter of 112.8 mm. All samples were allowed to equilibrate in TAPPI conditions for at least 24 h prior to completion of the TSA test. After conditioning, each sample was tested as is, i.e., the multi-ply product was tested without separating the samples into individual ply. Fix the sample and start the measurement via PC. The PC records, processes and stores all data according to standard TSA protocols. The TS750 values recorded are the average of five iterations, once for each new sample.

Yes

Base using the aerated dry papermaking process generally described in U.S. Patent No. 5,607,551, commonly referred to as "Uncreped Aerated Drying ("UCTAD") and incorporated herein in a manner consistent with the present invention. The sheets were made.Basesheets were produced with a target dry basis weight of about 25gsm.Then the basesheets were converted into embossed two-ply tissue products.

A three layer headbox was used to make the basesheet to form a web having a first outer layer, also referred to as a fabric or fabric contact layer, an intermediate layer, and a second outer layer, also referred to as an air contact layer or air layer. . Using a variety of wood pulp fibers, including southern softwood kraft pulp (SSWK), eucalyptus hardwood kraft pulp (EHWK) and northern softwood kraft pulp (NSWK), various furnish layers as detailed in Table 3 below was formed. In certain cases, a debonding agent was added to the fabric contact layer and/or a dry strength resin was added to the interlayer as detailed in Table 3 below.

Sample first outer layer (wt%) mezzanine
(weight%) Second outer layer (wt%) Addition of Chemicals (kg/MT) Invention Examples 1-4 EHWK (30%) NSWK (40%) EHWK (30%) ProSoft® TQ-1003 (1.5)
FennoBond® 3300 (0.5) Invention Example 5 SSWK SSWK SSWK ProSoft® TQ-1003 (1.5)

Each furnish was diluted to a consistency of approximately 0.2%, transferred to a layered headbox, and deposited onto a Voith Fabrics TissueForm V forming fabric (commercially available from Voith Fabrics, Appleton, Wis.). The wet web was vacuum dewatered to a consistency of approximately 25% and then rapidly transferred when transferred to a transfer fabric. The transfer fabric was the fabric described as "Fred" in US Pat. No. 7,611,607 (commercially available from Voith Fabrics, Appleton, Wis.). The rapid transfer rate was 28%. The web was then transferred to a Tissue Max EX breathable dry fabric (commercially available from Voith Fabrics, Appleton, Wis.). The web was dried with a vent dryer to produce a dried tissue web.

The dried tissue web was fed to a gravure printing line, similar to that shown in FIG. 3, running at about 1,000 feet/min, where a latex polymer was printed onto the surface of the sheet. The binder composition was varied for each of the sample codes as shown in Table 4 below. Each binder is commercially available from Wacker Polymers, LP (Allentown, PA).

Sample binder % solids Invention Example 1 Vinnapas™ EZ123 30 Invention Example 2 Vinnapas™ EP1133 15 Invention example 3 Vinnapas™ EP1133 30 Invention Example 4 Vinnapas™ EP1133 30 Invention Example 5 Vinnapas™ EP1133 30

Using NaOH, the pH of the latex based binder was adjusted to a pH of approximately 6.0 and mixed for approximately 5-30 minutes prior to use in a gravure printing operation. The viscosity of the latex-based binder was between 30 and 30 as measured at room temperature using a viscometer (Brookfield™ Synchro-lectric viscometer Model RVT, Brookfield Engineering Laboratories Inc., Stoughton, MA) using a #1 spindle operating at 20 rpm. It was in the 60 cps range.

The first side of the dried web was printed with the bonding composition using rotogravure directly in the pattern shown in FIG. 5 . The pattern includes three elongated hexagons having a length of about 0.02 inches (0.51 mm) and a width of about 0.006 inches (0.15 mm). After printing, the sheet was pressed against a rotating drum having a surface temperature of approximately 126° C. and then removed.

The printed creped tissue web was further transformed to produce a two-ply tissue product. The individual tissue webs were embossed and overlapped using an embossing lamination apparatus, such as that described in US Pat. No. 3,867,225. The individual plies were arranged such that the surfaces printed with the binder composition formed the two outer surfaces of the two-ply tissue product.

After embossing and lamination, the two-ply tissue product was treated with a softening composition. The content of the softening composition is provided in Table 5 below.

softening composition number 1 Softening composition number 2 Silicone (wt%) 22.5 2 Glycerin (wt%) - 6 Nonionic surfactant (wt%) 7.5 5 PEG-1,000 (wt%) - 7 water (wt%) 70 80

The softening composition was applied by offset gravure printing. Addition levels when controlled by varying the gravure roll cell volume (BCM—measured in billions of cubic microns per square inch), as described in Table 6 below.

Sample softening composition Gravure Roll Cell Volume Invention Example 1 One 6 BCM Invention Example 2 One 4 BCM Invention example 3 2 6 BCM

The printed creped tissue multi-ply web was wound onto a core and converted into a multi-ply rolled tissue product, which was subjected to additional physical testing as summarized in Tables 7 and 8 below.

Sample basis weight (gsm) Caliper (μm) Seat Bulk (cc/g) GMT (g/3") Slough (mg) GM slope (kg) Stiffness index TS750 Invention Example 1 54.6 454 9.1 1255 0.6 8.13 6.5 28.3 Invention Example 2 53.8 445 8.3 1250 0.3 8.03 6.4 31.3 Invention example 3 57.4 508 8.9 1631 1.18 8.50 5.2 20.8 Invention Example 4 48.7 541 11.1 956 1.48 4.91 5.1 25.6 Invention Example 5 54.6 678 12.4 1178 1.18 5.07 4.3 22.4

Sample GM TEA
(g·cm/cm ² ) burst (gf) GM tear (gf) tear index TEA Index burst index durability index Invention Example 1 17.2 897 13.79 1.10 1.37 7.15 9.62 Invention Example 2 15.9 1003 16.11 1.86 1.27 8.02 11.16 Invention example 3 27.4 1607 23.24 1.42 1.68 9.85 12.96 Invention Example 4 14.5 951 15.80 1.65 1.52 9.94 13.12 Invention Example 5 18.9 1328 28.88 2.45 1.61 11.28 15.34

Example

Embodiment 1 : A creped multi-ply tissue product comprising first and second tissue ply, the product having a GMT of about 800 to about 1,700 g/3" and a slough of about 0.25 to about 2.00 mg. product.

Example 2 : The article of Example 1, having a durability index of from about 10.0 to about 20.0.

Example 3 : The article of Example 1 or 2, having a first outer surface and a non-crosslinked latex polymer disposed thereon.

Example 4 : The creping composition of any of Examples 1-3, consisting essentially of a non-crosslinked vinyl acetate-ethylene polymer disposed over the first or second ply of tissue and optionally an anti-blocking agent. A product comprising In certain embodiments, the creping composition may include a polysaccharide or a surfactant.

Example 5 : The article of any one of Examples 1-4, having a TS750 value of less than about 40.0.

Example 6 : The article of any one of Examples 1-5, having a rupture index greater than about 8.0.

Example 7 : The article of any one of Examples 1-6, having a dry rupture greater than about 1,000.

Example 8 : The article of any of Examples 1-7, having a stiffness index of from about 4.0 to about 10.0.

Example 9 : The article of any one of Examples 1-8, having a TEA index greater than about 1.50.

Example 10 The article of any of Examples 1-9, wherein the first and second creped tissue ply is air dried.

Example 11 : The polyhydroxy compound, diamidoamine quaternary compound, ester of any one of Examples 1-10 having a molecular weight of at least about 1,000 g/mole disposed on the first or second outer surface An article comprising an emollient selected from the group consisting of a quaternary compound, an alkoxy alkyl quaternary compound, a benzyl quaternary compound, an alkyl quaternary compound, an imidazolinium quaternary compound, a polysiloxane, glycerin, and combinations thereof.

Embodiment 12 : The article of any of embodiments 1-11, further comprising a plurality of embossments disposed on the first or second ply of tissue.

Embodiment 13: The thirteenth embodiment , further comprising a plurality of perforations disposed on the first and second plys of tissue, wherein the article is helically wound around a core according to any of embodiments 1-12. Product, which is a spirally wound bathroom tissue roll containing two tissue folds.

Example 14 : The article of any one of Examples 1-13, having a basis weight of about 45 to about 60 gsm.

Example 15 : The article of any one of Examples 1-14, having a durability index of from about 10.0 to about 20.0.

Claims (29)

A creped multi-ply tissue product comprising first and second creped tissue ply, wherein the product has a geometric mean tensile strength (GMT) greater than about 700 g/3″ and a slaw less than about 2.00 mg. Pinged multi-ply tissue products. The creped multi-ply tissue product of claim 1 , having a GMT of from about 800 to about 1,700 g/3″. The creped multi-ply tissue product of claim 1 , having a GMT of from about 900 to about 1,500 g/3″. The creped multi-ply tissue product of claim 1 , having from about 0.25 to about 1.50 mg of slaw. The creped multi-ply tissue product of claim 1 , having a basis weight of about 45 to about 60 g/m ² (gsm) and a slaw of about 0.25 to about 2.00 mg. The creped multi-ply tissue product of claim 1 , having a durability index of about 10.0 to about 20.0 and a stiffness index of about 4.0 to about 8.0. The creped multi-ply tissue product of claim 1 , further comprising a plurality of embossments disposed on the first or second creped tissue ply. The creped multi-ply tissue product of claim 1 , wherein the first and second tissue ply are air dried. a first outer surface comprising a plurality of embossed portions disposed thereon and a non-crosslinked latex polymer, and a second outer surface comprising a plurality of embossed portions disposed thereon and a non-crosslinked latex polymer; A rolled tissue product comprising a spirally wound embossed, multi-ply tissue web, said product having a basis weight of from about 45 to about 60 gsm, a GMT of from about 700 to about 1,500 g/3", a slough from about 0.10 to about 2.00 mg. having a, roll-type tissue product. 10. The creped multi-ply tissue product of claim 9, having from about 0.25 to about 1.50 mg of slaw. 10. The creped multi-ply tissue product of claim 9, having a durability index of from about 10.0 to about 20.0. 10. The creped multi-ply tissue product of claim 9, wherein the tissue web comprises first and second creped and air-dried tissue ply. 10. The creped multi-ply tissue product of claim 9, wherein the tissue web has a stiffness index of from about 4.0 to about 8.0. 10. The creped multi-ply tissue product of claim 9, wherein the tissue web has a geometric mean slope of about 6.5 to about 8.5 kg. A creped multi-ply tissue product comprising first and second tissue ply and a plurality of embossments disposed on the first or second tissue ply, wherein the product has a GMT of from about 700 to about 1,500 g/3″; A creped multi-ply tissue product having from about 0.25 to about 1.50 mg of slaw. 16. The creped multi-ply tissue product of claim 15, having a durability index of from about 10.0 to about 20.0. 16. The creped multiplicity of claim 15, further comprising a creping composition consisting essentially of a non-crosslinked vinyl acetate-ethylene polymer disposed on the first or second tissue ply and optionally an anti-blocking agent. fold tissue products. 18. The creped multi-ply tissue product of claim 17, wherein the creping composition consists of an anti-blocking agent such as a polysaccharide or a surfactant. 18. The creped multi-ply tissue product of claim 17, wherein the vinyl acetate-ethylene polymer is carboxylated. A creped multi-ply tissue product comprising first and second creped tissue ply, wherein the product has a GMT of from about 700 to about 1,500 g/3″ and a TS750 value of less than 40.0. product. 21. The creped multi-ply tissue product of claim 20, having a TS750 value of from about 15.0 to about 40.0. 21. The creped multi-ply tissue product of claim 20, having a stiffness index of less than about 10.0. 21. The creped multi-ply tissue product of claim 20, having a stiffness index of from about 5.0 to about 10.0. 21. The creped multi-ply tissue product of claim 20, having a stiffness index of from about 5.0 to about 7.5. 21. The creped multi-ply tissue product of claim 20, having a geometric mean slope of from about 6.5 to about 8.5 kg. 21. The creped multi-ply tissue product of claim 20, wherein the first or second creped tissue ply comprises a plurality of embossments. 21. The creped multi-ply tissue product of claim 20, having first and second outer surfaces and a non-crosslinked vinyl acetate-ethylene polymer disposed on the first and second outer surfaces. 28. The creped multi-ply tissue product of claim 27, further comprising an anti-blocking agent selected from the group consisting of polysaccharides and surfactants disposed on the first and second outer surfaces. 28. The polyhydroxy compound of claim 27, wherein the polyhydroxy compound, diamidoamine quaternary compound, ester quaternary compound, alkoxy alkyl quaternary compound, has a molecular weight of at least about 1,000 g/mole disposed on the first or second outer surface; A creped multi-ply tissue product, further comprising an emollient selected from the group consisting of benzyl quaternary compounds, alkyl quaternary compounds, imidazolinium quaternary compounds, polysiloxanes, glycerin, and combinations thereof.

Images